I’ve learned a little by trial and error, trying things. One thing is that the principles are the same, whether you’re painting a StuG or a French hussar [;)] That is, I’ll use a darker shade of the field color when coloring panel lines, than just to put black in it. If the field is dark mustard yellow, I might use a medium brown for that panel line.
I look at shading on a face the same way. For Caucasian faces, for example, I like to use Andrea Beige, or Vallejo’s light skin colors, for a base. Then, I’ll take a burnt siena and add a tiny drop to some of that base color, mix it thoroughly, and then apply that to the folds on the face–the bags under the eyes, for example, or in the lines from the corners of the mouth up the sides of the nose. Just like doing a panel line.
And then, if I’m using acrylics for the base, I might use acrylics for the shading, in which case I thin the shade color and just keep applying it, building up the color a little at a time, till it looks right to my eye. Or, I might use oils for shading over the acrylic base. In that case, I’ll mix a shade color, again, looking at my base and then picturing it a little darker, even to the point of looking in the mirror to help visualize it, and then I apply the oils to the folds. Now, the beauty part about using the oils is their slow drying time, so I can wipe away the excess, leaving the color in the folds, and I can also use the brush to remove the color, brushing towards the lighter areas, and creating a blended transition from the highlight to the shadow.
Generally, with Caucasian complexions, I find a medium brown or tan to be very useful to use as the basis of the shadow. For black complexions, I tend to work in the other direction, that is, applying a darker base color and then using a lighter shade of that color and hitting the highlights, like the cheekbones, the bridge of the nose, the forehead, chin.
I hope that sounds clear. In any case, please do keep painting! I think you’ll find it gets less intimidating and you develop a technique, the more you do it.